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By J. M. Roberts, D. M. Barnett

The activation energy required to break a pinned dislocation line away from its condensed atmosphere of impurity atoms is calculated as a .function of applied stress, without neglecting line tension. Reasows are presented for not assuming the effect of line tension to be negligible when considering the problem of freeing a small segment of dislocation from an impurity atmosphere. The dislocation is considered to he pinned at each atomic size along its length and the pinning points are assumzed immobile. The development is a refinement of the origznal cottrell-bilby1 theory. The solution is compared to recent approximations developed by cottrell3 and Haasen5 in which line tension con- IN 1949 Cottrell and bilby1 considered the problem of determining the force required to pull a dislocation away from its condensed atmosphere of impurity atoms. They also examined the effect of thermal fluctuations on this force. The dislocation line was pictured as bowing out in a triangular loop under the action of an applied stress, and the activation energy necessary to free the dislocation from its atmosphere was calculated as a function of stress, line energy, and dislocation-solute atom interaction. siderations were neglected. A qualitative explanation of the yielding process in terms of the activation of Frank-Read sources is presented, but the lack of a realistic solution to the dynamic dislocation problem involved prevents an extension of the model at present. A self-consistent correlation between the present calculations and experimental data for delay time associated with yielding and the temperature dependence of the upper yield stress was made. Favorable agreement was noted. It is concluded that extension of the original Cottrell-~ilby' theory which includes line tension effects can just as well describe the yielding process as other approximations3,5 which neglect line tension. Cottrell and Bilby found the form of the activation energy vs stress curves to be almost independent of the line energy and the interaction energy (i.e., these parameters only affected the activation energy U by a scale factor). A check of the theory was accomplished by comparison with the experimental data of McAdam and Mebs2 for the lower yield stress as a function of temperature. cottrell,3 in 1957, attempted to obtain a simple closed-form solution for the activation energy as a function of stress by linearizing the quartic equation relating displacement of the dislocation line and applied stress. It was argued that since the contribution to the line energy/atomic plane of a dislocation is made by the long-range stress field of the dislocation through a term of the type (Gb3/2p)ln A/ro, where

Jan 1, 1963

By Paul J. Sirkegian

The problem of properly controlling the movements of underground trains in the Emma Nevada and Morris Brooks workings of the Consolidated Coppermines Corporation of Kimberly, Nev., became more complex as the rate of production increased. Ore from these mines, which are connected through a 7000-ft. single-track haulageway (Fig. I), is hoisted through the Emma Nevada shalt. All production to date has been from one level. Because of heavy ground, even on the main haulage horizon, experience has shown that it is necessary to have a minimum cross section in the drifts, thus making it impractical to have a double track system. In 1937, production was 3000 tons per day; in 1938 it was increased to 6000 tons per day and in 1940 to 9000 tons per day. Each increase necessitated a revision in the method of controlling the underground traffic. In 1937 the tramming signal system consisted of a few signal lights in the main haulage drift. These lights were two 100-watt bulbs in a metal box that had one green and one red lens on each side. The box was mounted on the underside of a drift cap timber and could be seen For a considerable distance. The lights were so arranged that all boxes showed either red or green at the same time and all were controlled by a magnetic contactor at the entrance to each lateral drift. When the lights showed green, the main haulage was clear of traffic and a train could enter it. As the motor entered the main haulage drift, the motorman pulled the cord of the magnetic contactor switch, thus changing all the main haulage lights to red, which indicated that no other train could use the main haulage until the first train had turned into a lateral drift. When a train left the main line, its motorman pulled the cord connected with the magnetic contactors, causing the haulage lights to show green again. This arrangement permitted only one train at a time to use the main haulage and thus limited the number of train trips per shift, but it was satisfactory when the ore handled was only 3000 tons per day. Second SystEM Installed With a gradual increase in production it became necessary to place a train dispatcher in charge of all trains. He controlled their movements orally, giving his orders direct or by mine phone, instructing them where to load, when to leave for the station and when to return. His objective was to group several trains traveling in the same direction. Because of the human element involved, some mistakes were made. The danger of a serious collision was always possible. There was a 90° turn and curve in the underground haulageway, therefore travel in this section was always dangerous if mistakes were made in directing traffic. To protect the train crew, particularly the rear switchman who rode the last car or caboose, a two-way push button and flash-signal system was installed on the

Jan 1, 1946

By W. J. Reagan

A survey of the literature on bottom-cast practice gives but Scant information as to some of the real facts concerning this most int'eresting method of steel manufacture, and some of the information available is very misleading. An exceptionally good description of this met,hod of pouring or teeming is to be found in an English publication2 on the heterogeneity of steel ingots. Quoting from this paper: (a) With bottom teeming, the metal rises steadily and progressively in the mold with the minimum possible agitation, the main force of the stream coming from the ladle being broken down or retarded by the down gate or runner. Further, the stream of metal from the ladle, under these conditions of casting, is invariably maintained at a much more continuous rate and is steadier than with top teeming. (b) In view of the facts referred to in (a) it follows that with bottom teeming the metal is not exposed to atmospheric oxidation to anything like the same degree as with top teeming. In this paper it is intended to detail briefly some of the advantages of bottom-cast practice and to discuss the possibilities of iron-oxide control in the basic open-hearth furnace. A description of the type of charge, ingot rnold set-up, etc., is found in detail in an earlier paper.3 Design of Ingot Molds In any kind of steel manufacture, ingot-mold design is important. L. H. Nelson4 lists in the order of their probable importance the following factors as influencing most the solidification of the ingot:

Jan 1, 1934

By Robert Sisselman

If we are lucky," says Hollis M. Dole, Assistant Secretary of the Interior, "coal, uranium and hydropower will provide us with maybe a third of the energy we require in 1985. The other two- thirds will have to be made available in liquid and gaseous form." Luck, however, may have run out, for if the facts and figures relating to supply and demand of natural gas over the next 20 years prove accurate, the United States may fall short in its attempts to bring the energy crisis under control. By the year 1990 the world will need to consume a minimum 150 quadrillion Btu of energy with gas requirements running as high as 42-43 trillion cu ft. By 1990, the U.S. alone will require 45-46 trillion cu ft. To meet anticipated demand, this country will have to overcome a deficiency of about 20 trillion cu ft since, by all pragmatic estimates, it will produce only 15-20 trillion cu ft of gas. The importation of natural gas into the U.S. will help but will not solve the problem. Adequate gas supplies will have to be supplied domestically. The Arctic, with its predicted huge reserves of gas, combined with imports of liquid natural gas (LNG) may provide as much as 15% of the 45-46 trillion figure, however, such reserves will not come into play as quickly as originally thought. The Alaskan gas fields, for instance, will provide a substantial supplement to domestic gas needs, but only after 1976.

Jan 10, 1972

By Waynw P. Myers

Electricity, as normally thought of by a layman's definition, is a man- made force that has no color, no odor, is not visible, cannot be heard, yet man can control it and make it perform his work for him. A person dare not cheat on it, for it then will master him. It has laws, rules, and regulations that must be strictly adhered to if it is to perform in the safest, most reliable, and economical manner. In the early days of coal mining the power source was man himself. Later man employed steam and compressed air to reduce his muscle power requirements needed in the extraction of coal. By the turn of the 20th century, electricity had become the most common source of power for the coal industry. Steam and compressed air are still found in use in isolated cases today for specific applications; however, they are rapidly being replaced by electricity. Electrical laws and regulations are quite extensive and somewhat complex for the proper generation and use of electricity. Man-made laws, rules, and regulations for the care and handling of electricity, designed for man's safety, are rigidly enforced by Mine Safety and Health Ad- ministration (MSHA), as well as the various state departments of mines. BACKGROUND Until recent years most underground coal mines used direct current exclusively for all movable and for some stationary equipment. Exceptions were for permanent pumps, tipple, fan, and outside buildings where alternating current was normally employed. However, over 60 years ago there were mines with dual systems. Alternating current was used for cutting machines, drills, and pumps ; direct current for locomotives. There were no other machines as these were hand-loading mines. Later, during early mechanization in the 1920s, alternating current was also applied to loading machines at some mines. Use of dual electric systems then declined until fairly recently when

Jan 1, 1981

By J. W. Halley, G. L. Plimpton

Because of the two distinct stages in the solidification of rimmed steel, segregation in the rimmed ingot is more complex than that in the killed or semikilled ingot. In the earlier stage, chemical reactions, resulting in evolution of gas and vigorous stirring of the metal, effect a degree of negative segregation unique to rimmed steel. The composition of this zone constitutes the principal quality advantage of this type of steel. In the later stage of solidification, after the evolution of gas has ceased, the segregation follows the general pattern of a more completely deoxidized steel. However, the composition of the liquid remaining after the first solidification stage varies markedly from that of the original melt, some constituents having been partially removed as reaction products while the concentration of others has been intensified by rejection from the metal solidifying in the first zone. The aim, from the standpoint of segregation, in rimmed steel of high quality is to effect a maximum negative segregation in the rim zone without excessive concentration of undesirable elements at the center of the ingot. To achieve this aim, the composition of the melt may be varied and the furnace and pouring practice may be adjusted within certain limits. It is the purpose of this study to discuss segregation in rimmed steel from the standpoint of the mechanisms that produce it and to survey the phases of open-hearth practice that influence those mechanisms. Mechanisms Producing Segregation The mechanisms that determine the degree of segregation in the rimmed ingot are closely interrelated, making it difficult to select the primary factors and to determine a satisfactory order for presenting them. For instance, the question of sulphur segregation is relatively simple, since sulphur is not directly involved in chemical reactions in the ingot; but its concentration in the rim zone is dependent not only on its original analysis in the melt, its segregation coefficient, and the freezing rate, but also on the rate of its removal from the impure film on the solidifying surface. This washing action involves all the factors (such as freezing rate, the carbon-oxygen product, pressure, etc.) that determine the rate of gas evolution and hence the efficiency of film removal. Sulphur distribution between the rim and core is affected by the volumetric ratio between the two zones, and its segregation in the core is a function not only of the freezing rate of the core but also of all the foregoing factors that determine its concentration in the metal when solidification of the core starts. To simplify the presentation, it is proposed to treat the mechanisms affecting segregation independently in this section, reserving a discussion of their over-all effects for the section in which actual segregation data are given. The factors affecting segregation will be treated in the following order: (I) differential solidification, (2) removal of constituents as

Jan 1, 1945

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By E. A. Holbrook

LOCAL yearly taxes levied on bituminous coal lands in Pennsylvania have become a cost of first importance to the coal industry of the State. In Pennsylvania there is no State tax on real estate, but local taxation of real estate furnishes the greater part of the revenue necessary for the small governmental unit, as counties, townships, boroughs, and local school, road, and poor districts. Coal in place in the ground, whether or not title thereto has been severed from ownership of the surface, is assessed as real estate and on its supposed sale or market value. There are eight classes of counties in Pennsylvania, based on population; in populous counties of the first, second and third class, assessments are made by a county board appointed by the county commissioners and are fairly uniform throughout the county. In counties of the fourth to the eighth classes inclusive, property assessments are made by property assessors elected by and for each township within a county. In these counties the board of county commissioners acts as a board of equalization and review to hear appeals. In most counties, therefore, where there is a large unmined reserve of coal, assessments on that coal vary for each township, irrespective of the fact that the coal bed is continuous under many townships.

Jan 1, 1933

By Masayuje Otagawa

The mining methods adopted in Japanese mines are less known to the mining world than those of other countries, owing to the geographical remoteness, but they present many features of interest to mining engineers. The Ashio copper mine is at the town of Ashio, in Tochigiken, about 109 mi. (175 km.) from Tokyo by the Imperial Government railroad. The area of the concession owned by the Furukawa Mining Co. is 5000 acres (5023 ha.). The mine was formerly divided into three, viz. Hon-ean, Kotaki, and Tsudo, which are distant 3 mi. (4.8 km.) from each other as shown in Fig. 1. However, in 1914, when the writer was general manager, the three mining plants were amalgamated into one with the result of simplifying the working projects and increasing the operating efficiency. The mine was visited by the Institute party in November, 1911, when K. Inouye was the general manager. Shortly afterward, the writer was appointed manager, and, in 1915, he was succeeded by Dr. K. Asano. At the end of 1917, K. Kibe became general manager and, after two years, was succeeded by the present manager, I. Sugimoto. For some time Dr. J. Kojima was acting general manager. It is necdless to say that the gentlemen mentioned are all members of the Institute, as is also Baron T. Furukawa, president of the company. Since the discovery of the enormous masses, called "kajika" or "bullhead" deposits, which the writer has described elsewhere,' the mining methods have been varied to meet the different conditions presented by these deposits. The Ashio Ore The country rock of this mine consists of the middle Chichibian slate and quartzite into which has been intruded a post-Tertiary plagio-liparite neck more than 2 mi. in diameter, in the shape of an inverted cone which narrows downward to a relatively small diameter in depth.

Jan 1, 1923

By R. F. Mehl, W. Batz, C. Wells

Diffusion coefficient values for carbon in austenite covering a wide range of temperature and composition have been determined employing statistical methods. In addition, the relation between concentration and each of the following, D (diffusion coefficient), Q (activation heat of diffusion), and A (the constant in the diffusion equation), has been obtained. A study of the rates of diffusion of austenite was published in Metals Technology in 1940.' The present investigation is an extension of the earlier work, undertaken (1) to obtain values of the coefficient of diffusion, D, over a much wider range of carbon concentration, and (2) to provide data in all ranges of concentration and temperature in such abundance that statistical methods could be employed to evaluate the accuracy of the data with unusual precision. Composition of Materials: Composition of materials used in this research program are listed in table I. These materials, all forged to about 1 1/4 in. rounds, consist of a high-purity iron, Armco iron, a large number of laboratory-made plain carbon steels containing amounts of impurities normally expected in high-quality commercial steels, and three silicon steels. Since it was known at the time these steels were being made that impurities in the amounts present were unlikely to affect carbon diffusion rates' significantly, the effort made to obtain high-purity steels was not as persistent as it otherwise would have been. Procedure: In general, the procedure followed by Wells and Mehl and described' in detail in an earlier publication' is the one used by the present authors. However, certain modifications have been made which it is believed allow diffusion data to be interpreted more objectively and correctly. These are described completely under appropriate subheadings which follow. Experimental Procedure: Experimental procedure includes (1) the preparation of specimens by welding steels of different carbon contents, (2) the heating of these for certain times at selected temperatures in order to diffuse carbon along the specimens across the welded "interface," and (3) the determination of the carbon distribution across the diffusion zone. Preparation of Specimens: Prior to welding steel of one carbon content to iron or steel of another carbon content, surfaces to be welded are machined perpendicular to the longitudinal axis of cylinders which are about 3/4 in. in diam and 1 1/2 in. long. The prepared, flat, parallel surfaces are brought together and butt-welded electrically. Evidence of a good weld is given in fig. 1. Welding temperature

Jan 1, 1951

By Masayuje Otagawa

The mining methods adopted in Japanese mines are less known to the mining world than those of other countries, owing to the geographical remoteness, but they present many features of interest to mining engineers. The Ashio copper mine is at the town of Ashio, in Tochigiken, about 109 mi. (175 km.) from Tokyo by the Imperial Government railroad. The area of the concession owned by the Furukawa Mining Co. is 5000 acres (5023 ha.). The mine was formerly divided into three, viz. Hon-ean, Kotaki, and Tsudo, which are distant 3 mi. (4.8 km.) from each other as shown in Fig. 1. However, in 1914, when the writer was general manager, the three mining plants were amalgamated into one with the result of simplifying the working projects and increasing the operating efficiency. The mine was visited by the Institute party in November, 1911, when K. Inouye was the general manager. Shortly afterward, the writer was appointed manager, and, in 1915, he was succeeded by Dr. K. Asano. At the end of 1917, K. Kibe became general manager and, after two years, was succeeded by the present manager, I. Sugimoto. For some time Dr. J. Kojima was acting general manager. It is necdless to say that the gentlemen mentioned are all members of the Institute, as is also Baron T. Furukawa, president of the company. Since the discovery of the enormous masses, called "kajika" or "bullhead" deposits, which the writer has described elsewhere,' the mining methods have been varied to meet the different conditions presented by these deposits. The Ashio Ore The country rock of this mine consists of the middle Chichibian slate and quartzite into which has been intruded a post-Tertiary plagio-liparite neck more than 2 mi. in diameter, in the shape of an inverted cone which narrows downward to a relatively small diameter in depth.

Jan 1, 1923

By A. B. Parsons

AN often repeated criticism of the profession of engineering is that it is as a whole it lacks solidarity. organization, co-ordination, and leadership. Significantly, the critic, are all engineers. Other members of the body politic either do not know about the absence of organization or they do not care. If engineers have no organization they have a plethora of organizations. There exist in the United State, today some 350 societies. institutes. clubs, associations, and councils of engineers and engineering technologists and this number excludes several hundred local chapters of national societies. trade associations, and local engineers' clubs of purely social character- Successful engineers must be proficient in analyzing, planning, and co-ordinating. but it is generally admitted that for their profession as a whole their success in this respect has been indifferent.

Jan 1, 1943

By Frank Milliken

IN September 1937, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1007 to 1019. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about I per cent Cu. The chief copper mineral, chalcocite, was dissemi-nated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was prob-ably less than 6o per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a com-plete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof com-prised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig. 1, which gives percentages of tonnage and copper content.

Jan 1, 1940

ALABAMA Aldrich -Thomas, D A Altoona -Cain, J Anmston-Cowie, L K Walmsley, W N White, H E Bankhead -Terentieff, V E Bessemer -Abbott, C E Ball, E M McKenzie, W C, Jr Mitchell, F R Morgan, C Thompson, N E Birmingham -Adams, J H Adler, J E Aldrich, T H Aldrich, T H , Jr

Jan 1, 1923

ALABAMA. Anniston.-Noble, A. E., 20th St. and Wilmer Ave. Auburn.-Brown, R. L., Box 0. Belle Ellen.-Hutcheson, W. C. Bessemer.-Abbott, C. E., T. C., I. & R.R. Co Dobbs, G. G., Box 97. Ferguson, V., U. S. C. I. Pipe & Fdy. Co. Williams, E. P., Tenn. C., 1. & R. R. Co. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr., 406 Woodward Bldg. Allen, A. W., 1616 S. 14th Ave. Bowron, J., 1401 S, 20th St. Burbidge, T. A., Brown-Marx Bldg. Coxe, E. H. Tenn. C., I. & R. R. Co. Crawford, C. G., Tenn. C., I. & R. R. Co. Crockard, F. H., Brown-Marx Bldg. Ellis, E. E.,1515 Brown-Marx Bldg. Fairbairn C. T., Woodward Bldg. Fies, M. H., 2316 Highland Ave. Geismer, H. S., Keiser-Geismer Engrg. Co.

Jan 1, 1917

By Kenneth A. Gutschick, Robert S. Boynton

Lime has become a very general loosely used term that includes virtually all finely divided types of limestone as well as burned forms of lime. However, actually (and according to Webster) lime is only calcined limestone (known as quicklime, calcium oxide, or calcia). It also embraces the secondary product of quicklime-namely hydrated lime or slaked lime (calcium hydroxide). Fundamentally there are two basic types of limestone-high calcium and high magnesium (dolomitic). The dolomitic quicklimes and hydrated limes correspond to their "high calcium" counterparts in terminology. The only difference is that the dolomitic types are a combination of the elements, calcium and magnesium, whereas high calcium limes contain only 0.5 to 2 pct of magnesium. Both types, which are made through calcination at high temperatures, are shown chemically as follows: [ ] In the above reactions either type of limestone is burned (calcined) in furnaces known as lime kilns so that the carbon dioxide content of the stone is expelled as a gas. With high calcium limestone 44 pct of the weight of the stone is lost; with dolomitic limestone the loss is 48 pct. Also, both reactions are chemically reversible since quicklime absorbs carbon dioxide readily and in so doing transforms itself back to the original carbonate form. Most quicklimes correspond in size to the original rock, which varies from one to eight inches, depending upon the type of kiln employed. Slight shrinkage occurs during calcination. A few limestones when calcined will decrepitate (break down) into a fine powdery form; however, chemically it is the same as the pebble or lump-sized material. For some uses the lumps of quicklime are pulverized and packaged. Since quicklime has great affinity for moisture and carbon dioxide, it is perishable. When it absorbs moisture and CO2 slowly from the atmosphere, the resulting product is "airslaked." Consequently, it must be stored in dry, moisture-proof areas that are free from CO2. Because of its fugitive nature, it is usually consumed within a few weeks after manufacture. A more stable form of lime is hydrated lime-commercially made by adding water to the quicklime until the lumps break down into a fine, white powder. This product, which is usually packaged, can be stored more safely; and many of its uses are interchangeable with quicklime. The irreversible chemical reactions of hydrated lime for both high calcium and dolomitic types are: [ ]

Jan 1, 1960

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By J. E. Johnson

(Cleveland Meeting, October, 11,1912.) THE subject of blast-furnace slag is one which has had much consideration, particularly from the scientific standpoint, and several years ago technical literature contained many learned discussions on the oxygen-ratio of the acids and the bases, all on the assumption that acids and bases must be present in a ratio depending on molecular weight and chemical valency. Much work has also been done, sometimes in conjunction with the former, on the total heat and the temperature of initial fusion or softening of various slags. A wider knowledge of the blast-furnace now enables us to say that for practical purposes this work has been of almost no value. It is now generally admitted that on the physical side the important point of a given slag is neither its total heat of fusion nor its softening-point, but its free-running temperature, since this is the critical temperature of the furnace. This temperature bears no definite relation to the softening-temperature, as determined by Seger cones, for instance, because some slags melt relatively like ice, with a very short viscous-range, while others melt relatively like tar, with a very long viscous-range. In one the difference between the softening- and the free-running temperature may be very small, as little as 100° F., while in another this difference may easily be 200° or 300°. The importance of this difference is so great in practice as to destroy completely the value of exhaustive investigations, even such as those of 0. Boudouard, published a few years ago.1 * Presented also at the Joint Meeting of the Institute with Section IIIa, Metallurgy and Mining, of the Eighth International Congress of Applied Chemistry, New York, September, 1912. 1 It may not be amiss at this point to call attention to the excellent suggestion of Woolsey McA. Johnson, made several years ago, for determining the temperature at which different slags have the same practical fusibility. This suggestion

Oct 1, 1912

By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954